Fragrance compositions containing norbornene derivatives

ABSTRACT

Embodiments in accordance with the present invention relate generally to a variety of norbornene derivatives exhibiting olfactive properties and are suitable as fragrance ingredients. More specifically, this invention relates to various fragrance compositions containing one or more of a compound of formula (I): 
     
       
         
         
             
             
         
       
     
     Wherein R 1 , R 2 , R 3  and R 4  are as defined herein. The compounds of formula (I) are useful as perfumes, colognes, and in perfume augmenting, modifying, enhancing, and imparting compositions. The compositions of this invention are therefore useful in a variety of products including perfumes, colognes, soaps, detergents, candles, air fresheners, trash bags, tissues, deodorants, lotions, skin care products, hair products, sanitary products, cleaning products, and the like.

This application is a continuation of U.S. application Ser. No.16/512,567, filed Jul. 16, 2019, now allowed, which claims the benefitof U.S. Provisional Application No. 62/698,453, filed Jul. 16, 2018,both of which are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION Field of the Invention

Embodiments in accordance with the present invention relate generally toa variety of norbornene derivatives exhibiting olfactive properties andare suitable as fragrance ingredients. More specifically, this inventionrelates to various fragrance compositions containing a variety offunctionalized norbornene (NB) compounds for use as perfumes, colognes,and in perfume augmenting, modifying, enhancing, and impartingcompositions. The compositions of this invention are therefore useful ina variety of perfumed products including but not limited to perfumes,colognes, soaps, detergents, candles, air fresheners, trash bags,tissues, deodorants, lotions, skin care products, hair products,sanitary products, cleaning products, and the like.

Description of the Art

A variety of fragrance compounds are used as perfumes in the market,several of which are derived from natural sources. However, a keydrawback of such natural sources is continuous sustained availability ofthe raw materials. Another drawback is that there is always a batch tobatch variation in the quality of the products. A further drawback ofsuch naturally occurring fragrance compounds is high cost associatedwith their purification because of low yield of isolation from theirnatural sources. It should also be noted that some of the naturallyoccurring fragrance compounds may be toxic to animals and people intheir natural state requiring tedious methodologies for their isolationand purification. See, for example, H. M. Berven, Fragrance, Vol. 42,46-64 (2017).

As a result, there has been a considerable research efforts to find newcost effective synthetic, non-toxic fragrance compounds and compositionsthat can meet the ever growing demand for such compounds/compositions.More importantly, such synthetically made fragrancecompounds/compositions are expected to maintain uniform product qualitywith no batch to batch variations, and can be tailored to beenvironmentally friendly. As a result, such synthetic fragrancecompounds/compositions may thus provide solution to changingenvironmental landscape, and may alleviate some of the environmentalconcerns by reducing waste generated by currently used purificationprocesses to make naturally occurring fragrance compounds.

U.S. Pat. No. 4,119,577 discloses certain substituted norbornane perfumecompositions. U.S. Pat. No. 4,374,054 discloses a variety of norborneneand norbornane carboxylic acid derivatives useful as perfumerycomponents. U.S. Pat. No. 4,128,509 discloses a fragrance compositioncontaining 1-(norborn-2-yl)-2-methyl-butan-3-ol, which supposedlyexhibits similar odor as that of a naturally occurring mixture of α- andβ-santalol, commonly found in sandalwood oil. See also, U.S. Pat. No.4,229,600. U.S. Pat. No. 4,218,347 discloses methyl substituted orunsubstituted norbornene aldehyde carboxylic acid esters suitable as aperfuming and/or a flavoring ingredient. U.S. Pat. No. 4,351,748discloses a series of norbornane and norbornene derivatives having epoxycarboxylic acid ester side chain, which are useful as perfumingingredients. Finally, U.S. Pat. No. 4,132,677 discloses perfumecompositions containing cyanoethylidenenorbornenes.

Thus, it is an object of this invention to provide a variety offunctionalized norbornene derivatives useful as fragrance components ina variety of perfumed products and perfumery applications.

Other objects and further scope of the applicability of the presentinvention will become apparent from the detailed description thatfollows.

SUMMARY OF THE INVENTION

It has now been found that a fragrance composition can be made using avariety of functionalized norbornene compounds of formula (I).Accordingly, there is provided a fragrance composition comprising:

-   -   a) an effective amount of at least one compound of formula (I)        in the form of any one of its enantiomers or a mixture thereof:

-   -   wherein:    -   at least one of R₁, R₂, R₃ and R₄ is selected from the group        consisting of: substituted or unsubstituted (C₃-C₈)cycloalkyl;        substituted or unsubstituted (CR₅R₆)_(a)(C₃-C₈)cycloalkyl;        substituted or unsubstituted phenyl;    -   a group of formula (A):

—Z—(CO)OR  (A);

-   -   a group of formula (B):

—Z—O(CO)R  (B);

-   -   a group of formula (C):

—Z—O(CO)OR  (C);

-   -   a group of formula (D):

—Z—CR₅((CO)OR)₂  (D); and

-   -   a group of formula (E):

—Z—OR  (E);

-   -   wherein:    -   Z is a bond or a group selected from the group consisting of:        (CR₅R₆)_(a), (CR₅R₆)_(a)—O—(CR₅R₆)_(b),        (CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),        (CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which        may be the same or different and each independently is 1 to 12;        -   R₅ and R₆ are the same or different and each independently            selected from the group consisting of hydrogen, methyl,            ethyl, linear or branched (C₃-C₆)alkyl,            perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,            (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,            (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,            perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₂-C₆)acyl,            hydroxymethyl, hydroxyethyl and linear or branched            hydroxy(C₃-C₆)alkyl;    -   R is selected from the group consisting of hydrogen, methyl,        ethyl, linear or branched (C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl,        (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,        (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, methoxy, ethoxy, linear or        branched (C₃-C₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy,        (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,        (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,        (C₆-C₁₀)aryl(C₁-C₆)alkoxy,        (C₂-C₄)alkenyl(C₆-C₁₀)aryl(C₁-C₆)alkoxy,        perfluoro(C₆-C₁₀)aryloxy, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy,        (C₂-C₆)acyl, hydroxymethyl, hydroxyethyl and linear or branched        hydroxy(C₃-C₆)alkyl; and    -   the remaining R₁, R₂, R₃ and R₄ is selected from the group        consisting of hydrogen, methyl, ethyl, linear or branched        (C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,        (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,        (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, methoxy, ethoxy, linear or        branched (C₃-C₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy,        (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,        (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,        (C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy, (C₂-C₆)acyl, hydroxymethyl,        hydroxyethyl and linear or branched hydroxy(C₃-C₆)alkyl;    -   with the proviso that when Z is a bond, R is not hydrogen,        methyl, ethyl, linear or branched (C₃-C₆)alkyl;    -   b) at least one ingredient selected from the group consisting of        a fragrance carrier and a fragrance base; and    -   c) optionally at least one fragrance adjuvant.

In another aspect of this invention there is further provided a methodto confer, enhance, improve or modify the odor properties of a perfumingcomposition or of a perfumed article, which method comprises adding tosaid composition or article an effective amount of at least one compoundof formula (I) in the form of any one of its enantiomers or a mixturethereof.

DETAILED DESCRIPTION

The terms as used herein have the following meanings:

As used herein, the articles “a,” “an,” and “the” include pluralreferents unless otherwise expressly and unequivocally limited to onereferent.

Since all numbers, values and/or expressions referring to quantities ofingredients, reaction conditions, etc., used herein and in the claimsappended hereto, are subject to the various uncertainties of measurementencountered in obtaining such values, unless otherwise indicated, allare to be understood as modified in all instances by the term “about.”

Where a numerical range is disclosed herein such range is continuous,inclusive of both the minimum and maximum values of the range as well asevery value between such minimum and maximum values. Still further,where a range refers to integers, every integer between the minimum andmaximum values of such range is included. In addition, where multipleranges are provided to describe a feature or characteristic, such rangescan be combined. That is to say that, unless otherwise indicated, allranges disclosed herein are to be understood to encompass any and allsub-ranges subsumed therein. For example, a stated range of from “1 to10” should be considered to include any and all sub-ranges between theminimum value of 1 and the maximum value of 10. Exemplary sub-ranges ofthe range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8,and 5.5 to 10, etc.

As used herein, the bond symbol “

” in various structures shown below denotes that the stereochemistry atthis position is not determined and may constitute all possiblestereoisomers, including “exo” or “endo” isomers. Accordingly whenever astructure shown with the symbol “

” means that it includes all possible stereoisomers at thatconfiguration.

The expression “stereoisomers” is a general term used for all isomers ofthe individual molecules that differ only in the orientation of theiratoms in space. Typically it includes mirror image isomers that areusually formed due to at least one asymmetric center, (enantiomers). Inaddition, as noted above, the compounds of formula (I) may exist in twodifferent forms “exo” and “endo” configurations merely because of theirspatial orientation. Where the compounds according to the inventionpossess two or more asymmetric centers, they may additionally exist asdiastereoisomers, also certain individual molecules may exist asgeometric isomers (cis/trans). Similarly, certain compounds of thisinvention may exist in a mixture of two or more structurally distinctforms that are in rapid equilibrium, commonly known as tautomers.Representative examples of tautomers include keto-enol tautomers,phenol-keto tautomers, nitroso-oxime tautomers, imine-enamine tautomers,etc. It is to be understood that all such isomers and mixtures thereofin any proportion are encompassed within the scope of the presentinvention.

As used herein, the expression “alkyl” means a saturated, straight-chainor branched-chain hydrocarbon substituent having the specified number ofcarbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl,isopropyl, tert-butyl, and so on. Derived expressions such as “alkoxy”,“thioalkyl”, “alkoxyalkyl”, “hydroxyalkyl”, “alkylcarbonyl”,“alkoxycarbonylalkyl”, “alkoxycarbonyl”, “diphenylalkyl”, “phenylalkyl”,“phenylcarboxyalkyl” and “phenoxyalkyl” are to be construed accordingly.

As used herein, the expression “cycloalkyl” includes all of the knowncyclic groups. Representative examples of “cycloalkyl” includes withoutany limitation cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, and the like. Derived expressions such as“cycloalkoxy”, “cycloalkylalkyl”, “cycloalkylaryl”, “cycloalkylcarbonyl”are to be construed accordingly.

As used herein, the expression “perfluoroalkyl” means that all of thehydrogen atoms in said alkyl group are replaced with fluorine atoms,again having the specified number of carbon atoms. Illustrative examplesinclude trifluoromethyl and pentafluoroethyl, and straight-chained orbranched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl andtridecafluorohexyl groups. Derived expression, “perfluoroalkoxy”, is tobe construed accordingly. It should further be noted that certain of thealkyl groups as described herein, such as for example, “alkyl” maypartially be fluorinated, that is, only portions of the hydrogen atomsin said alkyl group are replaced with fluorine atoms and shall beconstrued accordingly.

As used herein, the expression “aryl” means substituted or unsubstitutedaromatic groups such as phenyl, naphthyl, anthracenyl, and the like.Specific examples of substituted phenyl or naphthyl include o-, p-,m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc.“Substituted phenyl” or “substituted naphthyl” also include any of thepossible substituents as further defined herein or one known in the art.

As used herein, the expression “arylalkyl” means that the aryl asdefined herein is further attached to alkyl as defined herein.Representative examples include benzyl, phenylethyl, 2-phenylpropyl,1-naphthylmethyl, 2-naphthylmethyl and the like.

As used herein, the expression “alkenyl” means a non-cyclic, straight orbranched hydrocarbon chain having the specified number of carbon atomsand containing at least one carbon-carbon double bond, and includesethenyl and straight-chained or branched propenyl, butenyl, pentenyl andhexenyl groups. Derived expression, “arylalkenyl” and five membered orsix membered “heteroarylalkenyl” is to be construed accordingly.Illustrative examples of such derived expressions includefuran-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

As used herein the expression “acyl” shall have the same meaning as“alkanoyl”, which can also be represented structurally as “R—CO—,” whereR is an “alkyl” as defined herein having the specified number of carbonatoms. Additionally, “alkylcarbonyl” shall mean same as “acyl” asdefined herein. Specifically, “(C₁-C₄)acyl” shall mean formyl, acetyl orethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as“acyloxy” and “acyloxyalkyl” are to be construed accordingly.

“Halogen” or “halo” means chloro, fluoro, bromo, and iodo.

In a broad sense, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a few of the specificembodiments as disclosed herein, the term “substituted” meanssubstituted with one or more substituents independently selected fromthe group consisting of (C₁-C₆)alkyl, (C₂-C₆)alkenyl,(C₁-C₆)perfluoroalkyl, phenyl, hydroxy, —CO₂H, an ester, an amide,(C₁-C₆)alkoxy, (C₁-C₆)thioalkyl and (C₁-C₆)perfluoroalkoxy. However, anyof the other suitable substituents known to one skilled in the art canalso be used in these embodiments.

It should be noted that any atom with unsatisfied valences in the text,schemes, examples and tables herein is assumed to have the appropriatenumber of hydrogen atom(s) to satisfy such valences.

By the term “fragrance” or “fragrance compound” or “fragrancecomposition” is meant a compound or a composition that exhibitspleasant, lasting floral, fruity, woody, spicy, nutty, herbal aroma,which is useful in the preparation of fragrance compositions andperfumed products.

By the term “effective olfactory” or “effective olfactive” or “effectiveodoriferous” amount of a compound is meant a sufficient amount of thecompound to impart desirable sense of smell to the composition.

As used herein, the expression “fragrance carrier” or “fragrance base”means a non-toxic solvent, dispersant, excipient, adjuvant, or othermaterial which is mixed with the compound of formula (I) as describedherein in order to permit the formation of a fragrance composition, asfurther disclosed herein.

Accordingly, in accordance with the practice of this invention there isprovided a fragrance composition comprising:

-   -   a) an effective amount of at least one compound of formula (I)        in the form of any one of its enantiomers or a mixture thereof:

-   -   wherein:    -   at least one of R₁, R₂, R₃ and R₄ is selected from the group        consisting of: substituted or unsubstituted (C₃-C₈)cycloalkyl;        substituted or unsubstituted (CR₅R₆)_(a)(C₃-C₈)cycloalkyl;        substituted or unsubstituted phenyl;        -   a group of formula (A):

—Z—(CO)OR  (A);

-   -   -   a group of formula (B):

—Z—O(CO)R  (B);

-   -   -   a group of formula (C):

—Z—O(CO)OR  (C);

-   -   -   a group of formula (D):

—Z—CR₅((CO)OR)₂  (D); and

-   -   -   a group of formula (E):

—Z—OR  (E);

-   -   wherein:    -   Z is a bond or a group selected from the group consisting of:        -   (CR₅R₆)_(a), (CR₅R₆)_(a)—O—(CR₅R₆)_(b),            (CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b),            (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b), (CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b),            where a and b are integers which may be the same or            different and each independently is 1 to 12;        -   R₅ and R₆ are the same or different and each independently            selected from the group consisting of hydrogen, methyl,            ethyl, linear or branched (C₃-C₆)alkyl,            perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,            (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,            (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,            perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₂-C₆)acyl,            hydroxymethyl, hydroxyethyl and linear or branched            hydroxy(C₃-C₆)alkyl;    -   R is selected from the group consisting of hydrogen, methyl,        ethyl, linear or branched (C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl,        (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,        (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, methoxy, ethoxy, linear or        branched (C₃-C₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy,        (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,        (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,        (C₆-C₁₀)aryl(C₁-C₆)alkoxy,        (C₂-C₄)alkenyl(C₆-C₁₀)aryl(C₁-C₆)alkoxy,        perfluoro(C₆-C₁₀)aryloxy, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy,        (C₂-C₆)acyl, hydroxymethyl, hydroxyethyl and linear or branched        hydroxy(C₃-C₆)alkyl; and    -   the remaining R₁, R₂, R₃ and R₄ is selected from the group        consisting of hydrogen, methyl, ethyl, linear or branched        (C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,        (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,        (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, methoxy, ethoxy, linear or        branched (C₃-C₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy,        (C₃-C₁₂)cycloalkoxy, (C₆-C₁₂)bicycloalkoxy,        (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,        (C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy,        perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy, (C₂-C₆)acyl, hydroxymethyl,        hydroxyethyl and linear or branched hydroxy(C₃-C₆)alkyl;    -   with the proviso that when Z is a bond, R is not hydrogen,        methyl, ethyl, linear or branched (C₃-C₆)alkyl;    -   b) at least one ingredient selected from the group consisting of        a fragrance carrier and a fragrance base; and    -   c) optionally at least one fragrance adjuvant.

The compounds employed in the composition of this invention arethemselves known in the literature or can be prepared by any of theknown methods in the art to make such or similar types of compounds. Ingeneral, the compounds of formula (I) can be prepared by employingcyclopentadiene and a suitable substituted olefin of formula (IA) andreacting them together under Diels Alder reaction conditions to form acompound of formula (I) as summarized in Scheme I.

The Diels Alder reaction is generally carried out at higher temperaturesin a closed reactor by mixing suitable amounts of cyclopentadiene with adesirable substituted olefin of formula (IA) which facilitates the(4π+2π) addition of the double bonds to form the compound of formula(I). Generally, such reactions are carried out in an autoclave at highertemperatures and optionally in the presence of a suitable solvent. Theresulting product is generally a mixture of exo- and endo-isomers offormula (I). These isomers may exhibit different olfactive propertiesand therefore, in some embodiments only one of the isomers may be moresuitable in the fragrance compositions of this inventions. In some otherembodiments both exo and endo isomers may be employed equally readily toform the olfactively effective fragrance compositions of this invention.

In some embodiments the fragrance composition according to the presentinvention contains one or more compounds of formula (I), wherein said atleast one of R₁, R₂, R₃ and R₄ is substituted or unsubstituted(C₃-C₈)cycloalkyl and the remaining R₁, R₂, R₃ and R₄ is selected fromthe group consisting of hydrogen, methyl, ethyl, linear or branchedpropyl, linear or branched butyl, CF₃, cyclohexyl, phenyl, benzyl,phenethyl, C₆F₅, methoxy, ethoxy, phenoxy, hydroxymethyl andhydroxyethyl.

Non-limiting examples of such compounds of formula (I) that can beemployed in the fragrance composition of this invention include allgeometric and stereoisomers of the following:

In yet some other embodiments the fragrance composition according to thepresent invention encompasses a compound of formula (I), wherein said atleast one of R₁, R₂, R₃ and R₄ is a group of formula (A):

—Z—(CO)OR  (A);

-   -   wherein:    -   Z is a bond or a group selected from the group consisting of:        -   (CH₂)_(a), (CH₂)_(a)—O—(CH₂)_(b), where a and b are integers            which may be the same or different and each independently is            1 to 4;    -   R is selected from the group consisting of methyl, ethyl, linear        or branched propyl, linear or branched butyl, CF₃, cyclohexyl,        phenyl, benzyl, phenethyl, C₆F₅, adamantyl and        methyladamantanyl;        -   and    -   the remaining R₁, R₂, R₃ and R₄ is selected from the group        consisting of hydrogen, hydrogen, methyl, ethyl, linear or        branched propyl, linear or branched butyl, CF₃, cyclohexyl,        phenyl, benzyl, phenethyl, C₆F₅, methoxy, ethoxy, phenoxy,        hydroxymethyl and hydroxyethyl.

Representative examples of such compounds of the formula (I) within thescope of this embodiment, without any limitation, including all possiblegeometric and stereoisomers, may be selected from the group consistingof:

In yet some other embodiments, the fragrance composition according tothe present invention encompasses a compound of formula (I), whereinsaid at least one of R₁, R₂, R₃ and R₄ is a group of formula (B):

—Z—O(CO)R  (B);

-   -   wherein:    -   Z is a bond or a group selected from the group consisting of:        -   (CH₂)_(a), (CH₂)_(a)—O—(CH₂)_(b), where a and b are integers            which may be the same or different and each independently is            1 to 4;    -   R is selected from the group consisting of methyl, ethyl, linear        or branched propyl, linear or branched butyl, cyclohexyl,        phenyl, benzyl, phenethyl, and —CH═CH—C₆H₄—OCH₃; and    -   the remaining R₁, R₂, R₃ and R₄ is selected from the group        consisting of hydrogen, hydrogen, methyl, ethyl, linear or        branched propyl, linear or branched butyl, CF₃, cyclohexyl,        phenyl, benzyl, phenethyl, C₆F₅, methoxy, ethoxy, phenoxy,        hydroxymethyl and hydroxyethyl.

Representative examples of such compounds of the formula (I) within thescope of this embodiment, without any limitation, including all possiblegeometric and stereoisomers, may be selected from the group consistingof:

In yet some other embodiments, the fragrance composition according tothe present invention encompasses a compound of formula (I), whereinsaid at least one of R₁, R₂, R₃ and R₄ is a group of formula (C):

—Z—O(CO)OR  (C);

-   -   wherein:    -   Z is a bond or a group selected from the group consisting of:        -   (CH₂)_(a), (CH₂)_(a)—O—(CH₂)_(b), where a and b are integers            which may be the same or different and each independently is            1 to 4;    -   R is selected from the group consisting of methyl, ethyl, linear        or branched propyl, linear or branched butyl, cyclohexyl,        phenyl, benzyl and phenethyl; and    -   the remaining R₁, R₂, R₃ and R₄ is selected from the group        consisting of hydrogen, hydrogen, methyl, ethyl, linear or        branched propyl, linear or branched butyl, CF₃, cyclohexyl,        phenyl, benzyl, phenethyl, C₆F₅, methoxy, ethoxy, phenoxy,        hydroxymethyl and hydroxyethyl.

Representative examples of such compounds of the formula (I) within thescope of this embodiment, without any limitation, including all possiblegeometric and stereoisomers, may be selected from the group consistingof:

In yet some other embodiments, the fragrance composition according tothe present invention encompasses a compound of formula (I), whereinsaid at least one of R₁, R₂, R₃ and R₄ is a group of formula (D):

—Z—CR₅((CO)OR)₂  (D);

-   -   wherein:    -   Z is a bond or a group selected from the group consisting of:        -   (CH₂)_(a), (CH₂)_(a)—O—(CH₂)_(b), where a and b are integers            which may be the same or different and each independently is            1 to 4;    -   R₅ is selected from the group consisting of hydrogen, methyl and        ethyl;    -   R is selected from the group consisting of methyl, ethyl, linear        or branched propyl, linear or branched butyl, cyclohexyl,        phenyl, benzyl and phenethyl; and    -   the remaining R₁, R₂, R₃ and R₄ is selected from the group        consisting of hydrogen, hydrogen, methyl, ethyl, linear or        branched propyl, linear or branched butyl, CF₃, cyclohexyl,        phenyl, benzyl, phenethyl, C₆F₅, methoxy, ethoxy, phenoxy,        hydroxymethyl and hydroxyethyl.

Representative examples of such compounds of the formula (I) within thescope of this embodiment, without any limitation, including all possiblegeometric and stereoisomers, may be selected from the group consistingof:

In yet some other embodiments, the fragrance composition according tothe present invention encompasses a compound of formula (I), whereinsaid at least one of R₁, R₂, R₃ and R₄ is a group of formula (E):

—Z—OR  (E);

-   -   wherein:    -   Z is a bond or a group selected from the group consisting of:        -   C(CH₃)₂, (CH₂)_(a), (CH₂)_(a)—O—(CH₂)_(b), where a and b are            integers which may be the same or different and each            independently is 1 to 4;    -   R is selected from the group consisting of methyl, ethyl, linear        or branched propyl, linear or branched butyl, cyclohexyl,        phenyl, benzyl and phenethyl; and    -   the remaining R₁, R₂, R₃ and R₄ is selected from the group        consisting of hydrogen, hydrogen, methyl, ethyl, linear or        branched propyl, linear or branched butyl, CF₃, cyclohexyl,        phenyl, benzyl, phenethyl, C₆F₅, methoxy, ethoxy, phenoxy,        hydroxymethyl and hydroxyethyl.

Representative examples of such compounds of the formula (I) within thescope of this embodiment, without any limitation, including all possiblegeometric and stereoisomers, may be selected from the group consistingof:

Various other compounds similar to compounds of formula (I) can also beemployed in the fragrance compositions of this invention. For example,the compounds of formula (I), wherein, either R₁ and R₂ or R₃ and R₄combined with the carbon atom to which they are attached to form acarbocyclic (C₃-C₇)ring optionally containing one or more heteroatomsselected from oxygen or nitrogen, and in addition a keto group so as toform either a lactone or a lactam ring. Representative examples of suchspiro compounds may be enumerated as follows:

In general, the fragrance compositions in accordance with the presentinvention encompass at least one of the above described compounds offormula (I) and if needed additional one or more compounds of formula(I) in order to provide the intended olfactive property to suchembodiments that are appropriate and desirable for the use for whichsuch embodiments are directed, thus such embodiments are tailorable to avariety of specific applications.

For example, as already discussed above, proper combination ofdistinctive monomers of formula (I) makes it possible to tailor acomposition having the desirable olfactive property having utility indifferent fragrance compositions. That is, depending upon the intendedapplications, including perfumed products, such as, perfumes, colognes,soaps, detergents, candles, air fresheners, trash bags, tissues,deodorants, lotions, skin care products, hair products, sanitaryproducts, cleaning products, etc., the compositions can be tailored toprovide such intended benefits.

Accordingly, there is further provided a perfuming compositioncomprising i) at least one compound of formula (I), as defined herein;ii) at least one ingredient selected from the group consisting of aperfumery carrier and a perfumery base; and iii) optionally at least oneperfumery adjuvant.

In some other embodiments, there is also provided a perfuming consumerproduct comprising: i) at least one compound of formula (I), as definedherein; and ii) a perfumery consumer base.

Any of the known perfumery consumer base that provide the intendedbenefit for such compositions can be employed in the perfuming consumerproduct according to the present invention. Exemplary perfumery consumerbase include but not limited to a perfume, a fabric care product, abody-care product, an air care product or a home care product.

In a further non-limiting examples of a perfuming consumer productaccording to the present invention encompasses a perfumery consumer baseselected from a fine perfume, a cologne, an after-shave lotion, a liquidor solid detergent, a fabric softener, a fabric refresher, an ironingwater, a paper, a bleach, a shampoo, a coloring preparation, a hairspray, a vanishing cream, a deodorant or antiperspirant, a perfumedsoap, shower or bath mousse, oil or gel, a hygiene product, an airfreshener, a “ready to use” powdered air freshener, a wipe, a dishdetergent or hard-surface detergent.

In an additional aspect of this invention there is further provided amethod to confer, enhance, improve or modify the odor properties of aperfuming composition or of a perfumed article, which method comprisesadding to said composition or article an effective amount of at leastone compound of formula (I), as defined herein, including the form ofany one of its enantiomers or a mixture thereof.

Any one or more of the specific compounds of formula (I) as describedhereinabove can be used in the method according to the presentinvention.

In a further embodiment of this invention, the composition contains anyof the fragrance carrier and a fragrance base and optionally at leastone fragrance adjuvant that would bring about the intended benefit.Generally, such suitable fragrance carriers include a suitable gaseousor liquid carriers, among others. Gaseous carriers are generally used inaerosol compositions and are inert to compositions of this invention.Non-limiting examples of gaseous carriers include air, nitrogen, carbondioxide, any suitable organic solvent, water, and the like.

The compounds of formula (I) may be used alone, as mixtures thereof, incombination with a fragrance carrier and/or a fragrance base material.As used herein, the “fragrance base material” includes all known odorantmolecules selected from the extensive range of natural products, andsynthetic molecules currently available, such as essential oils,alcohols, aldehydes and ketones, ethers and acetals, esters andlactones, macrocycles and heterocycles, and/or in admixture with one ormore ingredients or excipients conventionally used in conjunction withodorants in fragrance compositions, for example, carrier materials, andother auxiliary agents commonly used in the art.

As used herein, “fragrance composition” means any composition comprisingat least one compound of formula (I) and a fragrance base materialand/or a fragrance carrier. For example, a diluent conventionally usedin conjunction with odorants, such as dipropylene glycol (DPG),isopropyl myristate (IPM), triethyl citrate (TEC), alcohol (e.g.ethanol), and the like may be used as fragrance carrier.

Non-limiting examples of known odorant molecules, which may be combinedwith the compounds of formula (I) as herein defined include thefollowing: essential oils and extracts, e.g. castoreum, costus root oil,oak moss absolute, geranium oil, tree moss absolute, basil oil, fruitoils, such as bergamot oil and mandarine oil, myrtle oil, palmarose oil,patchouli oil, petitgrain oil, jasmine oil, rose oil, sandalwood oil,wormwood oil, lavender oil or ylang-ylang oil; alcohols, e.g. cinnamicalcohol, cis-3-hexenol, citronellol, EBANOL™, eugenol, farnesol,geraniol, SUPER MUGUET™, linalool, menthol, nerol, phenylethyl alcohol,rhodinol, SANDALORE™, terpineol or TIMBEROL™. Various known aldehydesand ketones used as fragrance compounds and/or fragrance enhancingcompounds, including but not limited to AZURONE®[7-(3-methylbutyl)-1,5-benzodioxepin-3-one], anisaldehyde,α-amylcinnamaldehyde, GEORGYWOOD™, hydroxycitronellal, ISO E® Super,ISORALDEINE®, HEDIONE®, LILIAL®, maltol, methyl cedryl ketone,methylionone, verbenone, or vanillin. Various known ether and acetalsused as fragrance compounds and/or fragrance enhancing compounds,including but not limited to AMBROX®, geranyl methyl ether, rose oxide,or SPIRAMBRENE®. Various known esters and lactones used as fragrancecompounds and/or fragrance enhancing compounds, including but notlimited to benzyl acetate, cedryl acetate, γ-decalactone, HELVETOLIDE®,γ-undecalactone or vetivenyl acetate; macrocycles, e.g. Ambrettolide,ethylene brassylate or EXALTOLIDE®. Various known heterocycles used asfragrance compounds and/or fragrance enhancing compounds, including butnot limited to isobutylchinoline.

The compounds according to formula (I) may be used in a broad range ofperfumed products, e.g. in any field of fine and functional perfumery,such as perfumes, air care products, household products, laundryproducts, body care products and cosmetics. The compounds can beemployed in widely varying amounts, depending upon the specificapplication and on the nature and quantity of other odorant ingredients,if employed. The proportion is typically from 0.1 to 10 weight percentof the application. In one embodiment, compounds of the presentinvention may be employed in a fabric softener in an amount of from0.001 to 0.1 weight percent. In another embodiment, compounds of thepresent invention may be used in fine perfumery in amounts from 0.01 to20 weight percent (e.g. up to about 10 weight percent). In some otherembodiments, between 0.01 and 5 weight percent. It should be notedhowever that these values are given only by way of example, since theexperienced perfumer may also achieve effects or may create intendedbenefit with lower or higher concentrations.

The compounds as described hereinabove may be employed in a consumerproduct base simply by directly mixing at least one compound of formula(I), or a fragrance composition with the consumer product base, or theymay, in an earlier step, be entrapped with an entrapment material, forexample, polymers, capsules, microcapsules and nanocapsules, liposomes,film formers, absorbents such as carbon or zeolites, cyclicoligosaccharides and mixtures thereof, or they may be chemically bondedto substrates, which are adapted to release the fragrance molecule uponapplication of an external stimulus such as light, enzyme, or the like,and then mixed with the consumer product base.

Thus, the invention additionally provides a method of manufacturing aperfumed product, comprising the incorporation of a compound of formula(I), as a fragrance ingredient, either by directly admixing the compoundto the consumer product base or by admixing a fragrance compositioncomprising a compound of formula (I), which may then be mixed with aconsumer product base, using conventional techniques and methods.Through the addition of an olfactory acceptable amount of at least onecompound of the present invention as hereinabove described the odornotes of a consumer product base will be improved, enhanced, ormodified.

Thus, the invention furthermore provides a method for improving,enhancing or modifying a consumer product base by means of the additionthereto of an olfactively acceptable amount of at least one compound offormula (I).

The invention also provides a perfumed product comprising: a) as odorantat least one compound of formula (I); and b) a consumer product base.

As used herein, “consumer product base” means a composition for use as aconsumer product to fulfill specific actions, such as cleaning,softening, and caring or the like. Examples of such products includefine perfumery, e.g. perfume and eau de toilette; fabric care, householdproducts and personal care products such as laundry care detergents,rinse conditioner, personal cleansing composition, detergent fordishwasher, surface cleaner; laundry products, e.g. softener, bleach,detergent; body-care products, e.g. shampoo, shower gel; air careproducts and cosmetics, e.g. deodorant, vanishing cream or lotion. Thislist of products is given by way of illustration, and is not to beregarded as being in any way limiting.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. In addition, one of skill in theart will readily appreciate that any such material be non-toxicespecially in a household product and otherwise non-deleteriousparticularly from an organoleptic standpoint whereby the ultimate flavorand/or aroma of the consumable material used is not caused to haveunacceptable aroma and taste nuances. Such materials may in general becharacterized as flavoring adjuvants or vehicles comprising broadlystabilizers, thickeners, surface active agents, conditioners, otherflavorants and flavor intensifiers.

Stabilizer compounds include preservatives, for example, sodiumchloride; antioxidants, such as for example, calcium and sodiumascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, turmeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include aldehydes, esters,natural oils, alcohols, sulfides, ketones, lactones, carboxylic acidsand hydrocarbons such as heliotropin, terpinenol-4, benzaldehyde, phenylacetaldehyde, benzyl formate, cis-3-hexenyl benzoate, methyl hexanoate,hexanal, eucalyptol, acetaldehyde, ethyl acetate, ethyl butyrate,turpentine gum oil, limonene, gum camphor, isobornyl acetate, borneol,cinnamic aldehyde, cuminic aldehyde, furfural, methyl cinnamate, cassiaoil, parahydroxybenzyl acetate, dimethyl sulfide, alphaionone, aceticacid, isobutyl acetate, acetone, butyric acid, formic acid, valericacid, amyl acetate, amyl butyrate, anethol, benzyl salicylate, diacetyl,dimethyl anthranilate, ethyl methylphenylglycidate, ethyl succinate,ethyl valerate, cis-3-hexen-1-ol, 2-hexenyl acetate, 2-hexenyl butyrate,hexyl butyrate, 4-(p-hydroxyphenyl)-2-butanone, betaionone, isobutylcinnamate, lemon essential oil, methyl butyrate, methyl caproate, methyldisulfide, methyl p-naphthyl ketone, orris butter, rose absolute,terpenyl acetate, gamma-undecalactone, vanilla and alcohol.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., and should, (i) be organoleptically compatible with the compoundsof formula (I) of this invention by not covering or spoiling theorganoleptic properties (aroma and/or taste) thereof; (ii) benon-reactive with the compounds of formula (I) of this invention and(iii) be capable of providing an environment in which the compounds offormula (I) of this invention can be dispersed or admixed to provide ahomogeneous medium. In addition, selection of one or more flavoringadjuvants, as well as the quantities thereof will depend upon theprecise organoleptic character desired in the finished product. Thus, inthe case of flavoring compositions, ingredient selection will vary inaccordance with the ultimate product to which the flavor and/or aromaare to be imparted, modified, altered or enhanced.

The following examples are detailed descriptions of methods ofpreparation and use of compositions of the present invention. Thedetailed preparations fall within the scope of, and serve to exemplify,the more generally described methods of preparation set forth above. Theexamples are presented for illustrative purposes only, and are notintended as a restriction on the scope of the invention.

EXAMPLES

The following abbreviations have been used hereinbefore and hereafter indescribing some of the compounds, instruments and/or methods employed toillustrate certain of the embodiments of this invention:

NBCyHex—5-cyclohexylbicyclo[2.2.1]hept-2-ene;MeAdEsNB—2-methyladamantan-2-yl bicyclo[2.2.1]hept-5-ene-2-carboxylate;EPEsNB—ethyl 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoate;NBMeOAc—(bicyclo[2.2.1]hept-5-en-2-yl)methyl acetate;NBMeOCinnamate—(bicyclo[2.2.1]hept-5-en-2-yl)methyl3-(4-methoxyphenyl)acrylate;NBEtCarb—(bicyclo[2.2.1]hept-5-en-2-yl)methyl ethyl carbonate;NBdiEtMalonate—diethyl 2-((bicyclo[2.2.1]hept-5-en-2-yl)methyl)malonate;andNBXOH—2-(bicyclo[2.2.1]hept-5-en-2-yl)propan-2-ol.

Various compounds of formula (I) as described herein are eithercommercially available or can be readily prepared following theprocedures as described herein or following the procedures as reportedin literature, see for example, U.S. Pat. No. 4,374,054.

Example 1 Olfactive Evaluations

A panel of three perfumers evaluated various compounds of formula (I).Each of the panelists tested the samples essentially under sameatmospheric conditions. All materials were olfactively evaluated neatfrom glass jars. Liquid materials were also evaluated on blotter for a24 hour period. Evaluations included odor type, odor strength and odorcharacteristics. The results from these evaluations are summarized inTable 1.

TABLE 1 Sample Perfumer 1 Perfumer 2 Perfumer 3 NBCyHex Moderatelystrong Herbaceous, Floral note with buttery, nutty odor mushroomy, mintyconsistent fresh with mint overtones jasmine like odor freesia and lillyodor MeAdEsNB Moderately strong Moderate citrus Fresh sweet spicy spicypine odor (limey), piney and ginger note earth odor EPEsNB Moderatelystrong Fruity, ethereal Clean, consistent sweet fruity odor citrus odorfruity odor. not with green, woody very diffusive but and fatty notesgood tenacity NBMeOAc Nice fruity odor, Fruity odor with Fruity greenbanana apple with woody banana, green, odor, very diffusive notes, verydiffusive chamomile notes NBMeOCinnamate Moderately strong Fruity odorwith Bubble gum, nice sweet, fruity cherry-almond, sugary sweet odor,odor with floral marzipan notes also displays a red elements berry noteNBEtCarb A nutty, fruity odor Fruity floral odor Fruity pineapple withmint elements with green, banana, fatty waxy note violet notes with aninteresting floral aspect NBdiEtMalonate Moderately strong Fruity odorwith Ethereal “witch sweet, fruity odor apple notes hazel” initial notewith nice green, followed by melon and woody pleasant apple notes floralcharacter NBXOH Nice earthy, green Strong limey odor Earthy gassy odorodor with touches of mint and wood

Example 2 Personal Care/Air Care Product Formulation

A personal care product such as hand soaps, hand moisturizer, and thelike or air care product such as air fresheners can be made using theformulation as set forth below.

A suitable combination of five to ten parts by weight of a compound offormula (I) as summarized in Example 1 or a mixture of one or morecompounds as listed therein can be combined with a mixture containingten to fifteen parts by weight of hexyl cinnamic aldehyde, six to tenparts by weight of benzyl propionate, one to two parts by weight ofisoeugenol, one to two parts by weight of diethyl phthalate, six to tenparts by weight of linalool, six to ten parts by weight of benzylacetate, six to ten parts by weight of benzyl salicylate, six to tenparts by weight of must ambrette and any other suitable fragrance agentto form a formulation which can be used in any of the personal careproducts and/or air care products.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A fragrance composition comprising: a) aneffective amount of at least one compound of formula (I) in the form ofany one of its enantiomers or a mixture thereof:

wherein: at least one of R₁, R₂, R₃ and R₄ is a group of formula (C):—Z—O(CO)OR  (C); and wherein: Z is a bond or a group selected from thegroup consisting of: (CR₅R₆)_(a), (CR₅R₆)_(a)—O—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₃-C₆)alkyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl,perfluoro(C₆-C₁₀)aryl, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₂-C₆)acyl,hydroxymethyl, hydroxyethyl and linear or branched hydroxy(C₃-C₆)alkyl;R is selected from the group consisting of hydrogen, methyl, ethyl,linear or branched (C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, methoxy, ethoxy, linear or branched(C₃-C₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, (C₂-C₄)alkenyl(C₆-C₁₀)aryl(C₁-C₆)alkoxy,perfluoro(C₆-C₁₀)aryloxy, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl and linear or branchedhydroxy(C₃-C₆)alkyl; and the remaining R₁, R₂, R₃ and R₄ is selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, methoxy, ethoxy, linear or branched(C₃-C₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy, (C₂-C₆)acyl, hydroxymethyl,hydroxyethyl and linear or branched hydroxy(C₃-C₆)alkyl; with theproviso that when Z is a bond, R is not hydrogen, methyl, ethyl, linearor branched (C₃-C₆)alkyl; b) at least one ingredient selected from thegroup consisting of a fragrance carrier and a fragrance base; and c)optionally at least one fragrance adjuvant.
 2. The fragrance compositionaccording to claim 1, wherein: Z is a bond or a group selected from thegroup consisting of: (CH₂)_(a) and (CH₂)_(a)—O—(CH₂)_(b), where a and bare integers which may be the same or different and each independentlyis 1 to 4; R is selected from the group consisting of methyl, ethyl,linear or branched propyl, linear or branched butyl, cyclohexyl, phenyl,benzyl and phenethyl; and the remaining R₁, R₂, R₃ and R₄ is selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branchedpropyl, linear or branched butyl, CF₃, cyclohexyl, phenyl, benzyl,phenethyl, C₆F₅, methoxy, ethoxy, phenoxy, hydroxymethyl andhydroxyethyl.
 3. The fragrance composition according to claim 2, whereinsaid compound of formula (I) is:


4. The fragrance composition according to claim 2, wherein said compoundof formula (I) is:


5. A perfuming composition comprising i) at least one compound offormula (I), as defined in claim 1; ii) at least one ingredient selectedfrom the group consisting of a perfumery carrier and a perfumery base;and iii) optionally at least one perfumery adjuvant.
 6. A perfumingconsumer product comprising: i) at least one compound of formula (I), asdefined in claim 1; and ii) a perfumery consumer base.
 7. A perfumingconsumer product according to claim 5, wherein said perfumery consumerbase is a perfume, a fabric care product, a body-care product, an aircare product or a home care product.
 8. The perfuming consumer productaccording to claim 7, wherein said perfumery consumer base is a perfume.9. The perfuming consumer product according to claim 7, wherein saidperfumery consumer base is a fabric care product.
 10. The perfumingconsumer product according to claim 7, wherein said perfumery consumerbase is a body-care product.
 11. The perfuming consumer productaccording to claim 7, wherein said perfumery consumer base is an aircare product.
 12. The perfuming consumer product according to claim 7,wherein said perfumery consumer base is a home care product.
 13. Aperfuming consumer product according to claim 5, wherein said perfumeryconsumer base is a fine perfume, a cologne, an after-shave lotion, aliquid or solid detergent, a fabric softener, a fabric refresher, anironing water, a paper, a bleach, a shampoo, a coloring preparation, ahair spray, a vanishing cream, a deodorant or antiperspirant, a perfumedsoap, shower or bath mousse, oil or gel, a hygiene product, an airfreshener, a ready to use powdered air freshener, a wipe, a dishdetergent or a hard-surface detergent.
 14. The perfuming consumerproduct according to claim 13, wherein said perfumery consumer base is afine perfume, a cologne or an after-shave lotion.
 15. A perfumingconsumer product according to claim 13, wherein said perfumery consumerbase is a liquid or solid detergent, a fabric softener, a fabricrefresher or an ironing water.
 16. A perfuming consumer productaccording to claim 13, wherein said perfumery consumer base is a paperor a bleach.
 17. A perfuming consumer product according to claim 5,wherein said perfumery consumer base is a shampoo, a coloringpreparation, a hair spray, a vanishing cream, a deodorant orantiperspirant, a perfumed soap, shower or bath mousse, oil or gel, ahygiene product, an air freshener, a ready to use powdered airfreshener, a wipe, a dish detergent or a hard-surface detergent.
 18. Amethod to confer, enhance, improve or modify the odor properties of aperfuming composition or of a perfumed article, which method comprisesadding to said composition or article an effective amount of at leastone compound of formula (I) in the form of any one of its enantiomers ora mixture thereof:

wherein: at least one of R₁, R₂, R₃ and R₄ is a group of formula (C):—Z—O(CO)OR  (C); wherein: Z is a bond or a group selected from the groupconsisting of: (CR₅R₆)_(a), (CR₅R₆)_(a)—O—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)O—(CR₅R₆)_(b), (CR₅R₆)_(a)—O(CO)—(CR₅R₆)_(b),(CR₅R₆)_(a)—(CO)—(CR₅R₆)_(b), where a and b are integers which may bethe same or different and each independently is 1 to 12; R₅ and R₆ arethe same or different and each independently selected from the groupconsisting of hydrogen, methyl, ethyl, linear or branched (C₃-C₆)alkyl,perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl,(C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl,perfluoro(C₆-C₁₀)aryl, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, (C₂-C₆)acyl,hydroxymethyl, hydroxyethyl and linear or branched hydroxy(C₃-C₆)alkyl;R is selected from the group consisting of hydrogen, methyl, ethyl,linear or branched (C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl,(C₃-C₁₂)cycloalkyl, (C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl,(C₆-C₁₀)aryl, (C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, methoxy, ethoxy, linear or branched(C₃-C₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, (C₂-C₄)alkenyl(C₆-C₁₀)aryl(C₁-C₆)alkoxy,perfluoro(C₆-C₁₀)aryloxy, perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy,(C₂-C₆)acyl, hydroxymethyl, hydroxyethyl and linear or branchedhydroxy(C₃-C₆)alkyl; and the remaining R₁, R₂, R₃ and R₄ is selectedfrom the group consisting of hydrogen, methyl, ethyl, linear or branched(C₃-C₆)alkyl, perfluoro(C₁-C₁₂)alkyl, (C₃-C₁₂)cycloalkyl,(C₆-C₁₂)bicycloalkyl, (C₇-C₁₄)tricycloalkyl, (C₆-C₁₀)aryl,(C₆-C₁₀)aryl(C₁-C₆)alkyl, perfluoro(C₆-C₁₀)aryl,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkyl, methoxy, ethoxy, linear or branched(C₃-C₆)alkoxy, perfluoro(C₁-C₁₂)alkoxy, (C₃-C₁₂)cycloalkoxy,(C₆-C₁₂)bicycloalkoxy, (C₇-C₁₄)tricycloalkoxy, (C₆-C₁₀)aryloxy,(C₆-C₁₀)aryl(C₁-C₆)alkoxy, perfluoro(C₆-C₁₀)aryloxy,perfluoro(C₆-C₁₀)aryl(C₁-C₃)alkoxy, (C₂-C₆)acyl, hydroxymethyl,hydroxyethyl and linear or branched hydroxy(C₃-C₆)alkyl.
 19. The methodaccording to claim 18, wherein said compound of formula (I) is:


20. The method according to claim 18, wherein said compound of formula(I) is: